CN111346640B - Transition metal monoatomic-supported electrolyzed water catalyst and preparation method thereof - Google Patents
Transition metal monoatomic-supported electrolyzed water catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transition metal monoatomic-supported electrolyzed water catalyst and a preparation method thereof, belonging to the field of electrocatalysis. The invention utilizes electrostatic spinning fiber and phthalocyanine to jointly limit the domain to synthesize high-dispersion transition metal monoatomic atom, the electrolyzed water catalyst is composed of a carrier and a catalytic active component, the carrier is ultrafine carbon nanofiber, and the catalytic active component is transition metal monoatomic atom. The fiber-supported transition metal monoatomic water electrolysis catalyst prepared by the invention has the characteristics of high active site performance and good dispersibility, has good alkaline water electrolysis hydrogen evolution activity, and can be used as a self-supporting electrode material to be directly used for electrocatalytic hydrogen production.
Description
Technical Field
The invention relates to a transition metal monoatomic-supported electrolyzed water catalyst and a preparation method thereof, belonging to the electrocatalysis technology.
Background
With the continuous and deep industrialization process and the continuous consumption of fossil fuels, human beings face a huge dilemma of global energy shortage. The development of new energy is an important way to solve the current energy crisis, and hydrogen energy is widely concerned as a clean energy. Hydrogen production by water electrolysis is one of the most promising methods for producing hydrogen with high efficiency, convenience and the main mechanism thereof comprises two electrode reactions, namely a hydrogen evolution reaction at a cathode and an oxygen evolution reaction at an anode. In recent years, how to design and develop an electrode catalyst with excellent activity, good stability and high cost performance becomes the biggest technical bottleneck influencing the industrialization of hydrogen production by water electrolysis.
The electrocatalytic reaction only reacts on the surface of the nano catalyst, so that the adsorption of reactants on the surface of the catalyst and the desorption of products on the surface of the catalyst determine the catalytic efficiency to a great extent, and the reaction kinetics in the water electrolysis process can be effectively changed by regulating and controlling the size and the surface electronic structure of the nano catalyst, so that the hydrogen production performance of water electrolysis is improved. Recent studies have shown that as the size of nanoparticles is reduced to sub-nanometer dimensions, the number of non-coordinated metal atoms increases dramatically, providing a greater abundance of catalytically active sites. Particularly, when stable metal monoatomic is formed, the atom utilization rate reaches the maximum and approaches to 100 percent. In recent years, some transition metal monatomic catalysts have attracted considerable attention in electrocatalytic reactions, and various transition metal monatomic catalysts supported on a base material such as a metal oxide, a metal nitride, porous carbon, or a molecular sieve have been developed. The substrate material not only can stabilize the transition metal single-atom catalyst and provide good conductivity, but also can regulate and control the electronic structure of transition metal atoms through the interface action with metal, thereby further improving the catalytic performance. The reported methods for preparing transition metal monatomic catalysts are mainly: thermal deposition, hydrothermal, electrodeposition, photoreduction, templating, and the like. These preparation methods are relatively cumbersome and not conducive to mass production, and some methods require harsh conditions, which limits their practical applications.
So far, transition metal monatomic catalysts still have more problems in the field of hydrogen production by electrolyzing water, and the two main problems are two, one is the high-efficiency synthesis and regulation of active components of the catalysts; and the other is how to produce the transition metal monatomic catalyst in a large scale.
The electrostatic spinning technology is to prepare nano-micron fiber material by utilizing the breakdown effect of a high-voltage electrostatic field on a high molecular solution, and can produce the superfine carbon nanofibers in batches by further carbonization treatment. The superfine carbon nanofiber is a fibrous nano carbon material formed by curling multiple graphite sheets, has the characteristics of high strength, corrosion resistance, good electric and thermal conductivity, easiness in preparation and the like, and is very suitable for being used as a substrate material for preparing an electro-catalytic material.
Disclosure of Invention
The invention aims to provide a transition metal monoatomic supported electrolyzed water catalyst.
First, the present invention provides a method for preparing a transition metal monoatomic supported catalyst for electrolysis of water, comprising the steps of:
(1) dissolving a phthalocyanine complex and a ligand in a solvent, stirring for 0.5-1 h at 30-60 ℃ to obtain a uniform solution, adding a superfine nanofiber precursor into the solution, stirring for 5-8 h at 30-60 ℃ to obtain an electrostatic spinning solution, and preparing the electrostatic spinning solution into a phthalocyanine complex coupled fibrofelt by adopting an electrostatic spinning method;
(2) calcining the phthalocyanine complex coupled fiber mat: firstly, heating to 200-400 ℃, pre-oxidizing in air and preserving heat for 2-4 hours, then heating to 800-1200 ℃ under the protection of inert gas, preserving heat for 4-6 hours, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-supported transition metal monoatomic electrolytic water catalyst, wherein the molar ratio of the ligand to the phthalocyanine complex is 0-5: 1; the superfine nanofiber precursor accounts for 5-20% of the total mass of the electrostatic spinning solution; the metal in the phthalocyanine complex accounts for no more than 5 wt% of the electrolytic water catalyst.
In one embodiment of the present invention, the phthalocyanine complex is one or more of iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine, zinc phthalocyanine and manganese phthalocyanine.
In one embodiment of the invention, the ligand is one of glucose, phthalocyanine or bipyridine.
In an embodiment of the present invention, the superfine nanofiber precursor is one or more of polyacrylonitrile, polyvinyl alcohol, and polyvinylpyrrolidone.
In one embodiment of the present invention, the solvent is any one of dimethylformamide, ethanol or water.
In one embodiment of the present invention, the operating parameters of the electrospinning process are: the spinning voltage is 5-20 kV, the distance from the receiving device to the spinning needle is 4-15 cm, and the solution flow rate is 0.01-0.05 mL/min.
In one embodiment of the present invention, the inert gas is one of nitrogen and helium.
In one embodiment of the invention, the calcination is carried out by placing the phthalocyanine complex coupled fiber mat in a corundum boat, which is placed in the middle of a tube furnace.
In one embodiment of the present invention, the temperature increase rate during the calcination process is 1 to 5 ℃/min.
The invention also provides the fiber-supported transition metal monoatomic electrolytic water catalyst prepared by the method, which consists of a carrier and a catalytic active component, wherein the carrier is ultrafine carbon nanofiber, and the catalytic active component is transition metal monoatomic.
In one embodiment of the present invention, the transition metal single atom is one or more of Fe, Co, Ni, Cu, Zn or Mn, and the particle size thereof is less than 1 nm.
In one embodiment of the present invention, the diameter of the ultrafine carbon nanofibers is 50 to 500 nm.
Finally, the invention also provides the application of the water electrolysis catalyst in efficiently catalyzing water electrolysis and hydrogen evolution under the alkaline condition.
The invention has the following beneficial technical effects:
(1) the invention utilizes the synergistic confinement effect of the nano-fiber and the phthalocyanine to regulate and control the size of the transition metal nano-catalyst, develops a method for in-situ growth of a transition metal monoatomic atom by utilizing one-dimensional superfine nano-fiber, and simultaneously has stronger electronic coupling effect between the transition metal monoatomic atom and a fibrous carbon material, thereby further improving the catalytic activity.
(2) The electrolytic water catalytic material prepared by the invention has high-dispersion active components, high specific surface area and porosity and a highly stable catalyst structure, can effectively protect the active components from being corroded by electrolyte, and has good chemical stability and durability.
(3) The electrolytic water catalytic material prepared by the invention has high-dispersion active components, and the prepared electrolytic water catalytic material has good alkaline electrolytic water hydrogen evolution activity and stability, and is 10 mA-cm-1The overpotential of the transition metal reaches 120mV, which is smaller than most of the transition metal monoatomic ions reported at present, and after 5000 cycles, the overpotential of the transition metal is reduced by only 15mV without obvious reduction.
Drawings
FIG. 1 a microscopic topography of the fiber-supported iron monatomic electrolytic water catalyst prepared in example 1: (A) - (B) scanning electron micrographs at different magnifications; (C) (D) transmission electron micrographs at different magnifications.
FIG. 2 shows the hydrogen evolution polarization curve of the fiber-supported Fe atom-based electrolyzed water catalyst prepared in example 1 in 1M KOH.
Detailed Description
The technical scheme of the invention is further explained by the concrete implementation case and the attached drawings. In the invention, the raw materials, equipment and the like are all available from the market or are commonly used in the field, if not specially. The methods described in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) 57mg of iron phthalocyanine, 103mg of phthalocyanine and 7mL of dimethylformamide were mixed and stirred at 30 ℃ for 0.5 hour to obtain a uniform solution. Adding 0.9g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 12%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, preparing the electrostatic spinning solution into a phthalocyanine complex coupled fiber felt by adopting an electrostatic spinning method, controlling the spinning voltage to be 5kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 4cm, and controlling the solution flow rate to be 0.01 mL/min;
(2) placing the fiber felt coupled with the phthalocyanine complex in a corundum boat, placing the corundum boat in the middle of a tubular furnace, introducing air for pre-oxidation, heating the temperature of the tubular furnace to 280 ℃, keeping the temperature for 2 hours, then heating to 850 ℃ under the protection of nitrogen, keeping the temperature for 4 hours, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-loaded ferroelectric catalyst named as FePc/Pc-CNFs.
The micro-morphology of the prepared FePc/Pc-CNFs catalyst is shown in figure 1. As can be seen from the SEM images (A-B), the obtained catalyst has regular morphology, a diameter of about 200nm, a one-dimensional structure and is beneficial to the transmission of electrons; from the TEM images (C-D), it is found that the Fe active species are well dispersed in the fibers, and no significant agglomeration or large particles are observed, and the dispersibility is good.
The prepared FePc/Pc-CNFs catalyst is directly used as an electrode, the electrocatalytic hydrogen evolution activity of the FePc/Pc-CNFs catalyst is tested in a 1M potassium hydroxide solution, the obtained catalytic result is shown in figure 2, and the current density is 10 mA-cm-2The magnitude of the voltage to be applied, i.e., the value of the overpotential, is 120 mV.
In addition, glucose or 2, 2' -bipyridine is respectively selected as a ligand to replace phthalocyanine, the fiber-supported ferroelectric catalysts prepared by the method are named as FePc/Glu-CNFs and FePc/Bpy-CNFs respectively, the fiber-supported ferroelectric catalysts are directly used as electrodes respectively, the electrocatalytic hydrogen evolution activity of the fiber-supported ferroelectric catalysts is tested in a 1M potassium hydroxide solution, and the 10 mA-cm-mA hydrogen evolution activity is specifically considered-2The results are shown in Table 1. Under the condition of obtaining the same current density, the smaller the overpotential is, the higher the catalytic activity is, the better the hydrogen evolution performance is, and therefore, the electrocatalyst prepared by adopting the phthalocyanine as the ligand has the highest catalytic activity and the best hydrogen evolution capacity.
In addition, FePc/Pc-CNFs as catalyst was tested at 10mA cm after 5000 cycles of cyclic voltammetry on 1M potassium hydroxide solution-2The overpotential was reduced by only 15mV, and was not significantly reduced, indicating excellent stability and durability of the catalyst.
Table 1 electrolytic water activity of the electrocatalyst materials prepared with different ligands (phthalocyanine, glucose, 2, 2' -bipyridine): 10mA cm-2Over potential of
Example 2
(1) 57mg of iron phthalocyanine, 103mg of phthalocyanine and 7mL of DMF solution were mixed and stirred at 30 ℃ for 0.5 hour to obtain a uniform solution. Adding 0.9g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 12%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, preparing the electrostatic spinning solution into a phthalocyanine complex coupled fiber felt by adopting an electrostatic spinning method, controlling the spinning voltage to be 5kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 4cm, and controlling the solution flow rate to be 0.01 mL/min;
(2) placing a fiber felt coupled with a phthalocyanine complex in a corundum boat, placing the corundum boat in the middle of a tubular furnace, pre-oxidizing by introducing air, heating the temperature of the tubular furnace to 280 ℃, keeping the temperature for 2 hours, then heating to 750 ℃ or 950 ℃ under the protection of nitrogen, keeping the temperature for 4 hours, and finally cooling to room temperature under the protection of inert gas to obtain two fiber-loaded ferroelectric catalysts which are named as FePc/Pc-CNFs-750 and FePc/Pc-CNFs-950 respectively, directly using the fiber-loaded ferroelectric catalysts as electrodes, and testing the electrocatalytic oxygen evolution activity of the fiber-loaded ferroelectric catalysts in a 1M potassium hydroxide solution, wherein the obtained catalytic results are shown in Table 2.
Table 2 electrolytic water activity of the catalyst materials prepared in the present invention at different calcination temperatures (750 ℃, 850 ℃, 950 ℃): 10mA cm-2The overpotential is output.
Example 3
(1) 57mg of iron phthalocyanine and 7mL of DMF solution were mixed and stirred at 30 ℃ for 0.5 hour to obtain a homogeneous solution. Adding 0.9g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 12%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, preparing the electrostatic spinning solution into a phthalocyanine complex coupled fiber felt by adopting an electrostatic spinning method, controlling the spinning voltage to be 5kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 4cm, and controlling the solution flow rate to be 0.01 mL/min;
(2) placing the fiber felt coupled with the phthalocyanine complex in a corundum boat, placing the corundum boat in the middle of a tubular furnace, introducing air for pre-oxidation, heating the temperature of the tubular furnace to 280 ℃, keeping the temperature for 2 hours, then heating to 850 ℃ under the protection of nitrogen, keeping the temperature for 4 hours, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-loaded ferroelectric catalyst, namely FePc (0:1) -CNFs.
Selecting a molar ratio of phthalocyanine to iron phthalocyanine of 2:1 and 4:1, the other conditions and steps are consistent with those of example 3, the prepared fiber-supported ferroelectric catalysts are respectively named as FePc/Pc (1:2) -CNFs and FePc/Pc (1:4) -CNFs, the three are respectively and directly used as electrodes, the electrocatalytic hydrogen evolution activity of the three is tested in a 1M potassium hydroxide solution, and the 10mA cm/Pc electrocatalytic hydrogen evolution activity is specifically considered-2The results are shown in table 3, and it can be seen that when the molar ratio of phthalocyanine to iron phthalocyanine is 2:1, its catalytic activity is best.
Table 3 electrolytic water activity of catalyst materials with different ratios of phthalocyanine to phthalocyanine complex (0:1, 2:1, 4:1) in the present invention: 10mA cm-2The overpotential is output.
Example 4
(1) 283mg of copper phthalocyanine, 257mg of phthalocyanine and 7mL of DMF solution are mixed and stirred for 0.5h under 30 ℃ to obtain a uniform solution. Adding 0.9g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 12%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, preparing the electrostatic spinning solution into a phthalocyanine complex coupled fiber felt by adopting an electrostatic spinning method, controlling the spinning voltage to be 5kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 4cm, and controlling the solution flow rate to be 0.01 mL/min;
(2) placing the fiber felt coupled with the phthalocyanine complex in a corundum boat, placing the corundum boat in the middle of a tubular furnace, introducing air for pre-oxidation, heating the temperature of the tubular furnace to 280 ℃, keeping the temperature for 2 hours, then heating to 850 ℃ under the protection of nitrogen, keeping the temperature for 4 hours, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-loaded copper electrocatalyst.
Example 5
(1) 57mg of cobalt phthalocyanine, 205mg of phthalocyanine and 7mL of DMF solution were mixed and stirred at 30 ℃ for 0.5 hour to obtain a uniform solution. Adding 0.9g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 12%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, preparing the electrostatic spinning solution into a phthalocyanine complex coupled fiber felt by adopting an electrostatic spinning method, controlling the spinning voltage to be 5kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 4cm, and controlling the solution flow rate to be 0.01 mL/min;
(2) placing the fiber felt coupled with the phthalocyanine complex in a corundum boat, placing the corundum boat in the middle of a tubular furnace, introducing air for pre-oxidation, heating the temperature of the tubular furnace to 280 ℃, keeping the temperature for 2 hours, then heating to 850 ℃ under the protection of nitrogen, keeping the temperature for 4 hours, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-supported cobalt electrocatalyst.
Example 6
(1) 57mg of iron phthalocyanine, 103mg of phthalocyanine and 7mL of DMF solution were mixed and stirred at 30 ℃ for 0.5 hour to obtain a uniform solution. Adding 0.45g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 6%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, then preparing the electrostatic spinning solution into a phthalocyanine complex coupled fiber felt by adopting an electrostatic spinning method, controlling the spinning voltage to be 10kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 8cm, and controlling the solution flow rate to be 0.04 mL/min;
(2) placing the fiber felt coupled with the phthalocyanine complex in a corundum boat, placing the corundum boat in the middle of a tube furnace, introducing air for pre-oxidation, heating the tube furnace to 260 ℃, keeping the temperature for 1h, then heating to 1000 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, keeping the temperature for 4h, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-loaded ferroelectric catalyst.
Comparative example 1
(1) 35mg of iron acetylacetonate, 103mg of phthalocyanine and 7mL of a dimethylformamide solution were mixed and stirred at 30 ℃ for 0.5 hour to obtain a uniform solution. Adding 0.9g of polyacrylonitrile into the solution (the mass concentration of the polyacrylonitrile is 12%), stirring the mixture for 5 hours at 30 ℃ to obtain electrostatic spinning solution, preparing the electrostatic spinning solution into a fiber felt coupled with an iron complex by adopting an electrostatic spinning method, controlling the spinning voltage to be 5kV during electrostatic spinning, controlling the distance from a receiving device to a spinning needle head to be 4cm, and controlling the solution flow rate to be 0.01 mL/min;
(2) placing the fiber felt coupled with the iron complex in a corundum boat, placing the corundum boat in the middle of a tube furnace, introducing air for pre-oxidation, heating the tube furnace to 280 ℃, keeping for 2 hours, then heating to 850 ℃ under the protection of nitrogen, keeping for 4 hours, and finally cooling to room temperature under the protection of inert gas. The obtained nano-fiber has obvious Fe nano-particles, the diameter of the nano-particles is more than 5nm, and the size of the nano-particles is not uniform. The electrocatalytic oxygen evolution activity of the catalyst was tested in a 1M potassium hydroxide solution at 10 mA-cm-2The overpotential at (c) is 230 mV.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of a fiber-supported transition metal monoatomic water electrolysis catalyst is characterized by comprising the following steps:
(1) dissolving a phthalocyanine complex and a ligand in a solvent, stirring for 0.5-1 h at 30-60 ℃ to obtain a uniform solution, adding a superfine nanofiber precursor into the solution, stirring for 5-8 h at 30-60 ℃ to obtain an electrostatic spinning solution, and preparing the electrostatic spinning solution into a phthalocyanine complex coupled fibrofelt by adopting an electrostatic spinning method;
(2) calcining the phthalocyanine complex coupled fiber mat: firstly, heating to 200-400 ℃, pre-oxidizing in air and preserving heat for 2-4 h, then heating to 850 ℃ under the protection of inert gas, preserving heat for 4-6 h, and finally cooling to room temperature under the protection of inert gas to obtain the fiber-loaded transition metal monoatomic electrolytic water catalyst;
wherein the molar ratio of the ligand to the phthalocyanine complex is 2: 1; the superfine nanofiber precursor accounts for 5-20% of the total mass of the electrostatic spinning solution; the metal in the phthalocyanine complex accounts for no more than 5 wt% of the electrolytic water catalyst, the ligand is phthalocyanine, the superfine nanofiber precursor is one or more of polyacrylonitrile, polyvinyl alcohol and polyvinylpyrrolidone, and the phthalocyanine complex is one or more of iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, copper phthalocyanine, zinc phthalocyanine or manganese phthalocyanine.
2. The method for preparing the fiber-supported transition metal monatomic electrolyzed water catalyst according to claim 1, wherein the operating parameters of the electrospinning method are as follows: the spinning voltage is 5-20 kV, the distance from the receiving device to the spinning needle is 4-15 cm, and the solution flow rate is 0.01-0.05 mL/min.
3. The preparation method of the fiber-supported transition metal monatomic electrolytic water catalyst according to claim 1, wherein the temperature increase rate during the calcination process is 1 to 5 ℃/min.
4. The fiber-supported transition metal monatomic electrolytic water catalyst prepared by the method for preparing a fiber-supported transition metal monatomic electrolytic water catalyst according to any one of claims 1 to 3.
5. The fiber-supported transition metal monatomic electrolytic water catalyst according to claim 4, characterized in that it is composed of a support and a catalytically active component, wherein the support is an ultrafine carbon nanofiber, and the catalytically active component is a transition metal monatomic.
6. The fiber-supported transition metal monatomic electrolyzed water catalyst according to claim 5, wherein the diameter of the ultrafine carbon nanofibers is 50 to 500nm, and the particle size of the transition metal monatomic is less than 1 nm.
7. An electrolytic cell apparatus or an electrolytic water device comprising the fiber-supported transition metal monatomic electrolytic water catalyst according to any one of claims 4 to 6.
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